US3434797A - Process for treatment of hydrochloric acid waste pickle liquor - Google Patents
Process for treatment of hydrochloric acid waste pickle liquor Download PDFInfo
- Publication number
- US3434797A US3434797A US656364A US3434797DA US3434797A US 3434797 A US3434797 A US 3434797A US 656364 A US656364 A US 656364A US 3434797D A US3434797D A US 3434797DA US 3434797 A US3434797 A US 3434797A
- Authority
- US
- United States
- Prior art keywords
- pickle liquor
- hydrochloric acid
- iron
- waste pickle
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 235000021110 pickles Nutrition 0.000 title description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title description 20
- 239000002699 waste material Substances 0.000 title description 18
- 238000000034 method Methods 0.000 title description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000004571 lime Substances 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 11
- 235000011941 Tilia x europaea Nutrition 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 235000011167 hydrochloric acid Nutrition 0.000 description 9
- 235000013980 iron oxide Nutrition 0.000 description 8
- 239000007787 solid Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 159000000014 iron salts Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/01—Waste acid containing iron
Definitions
- This invention relates to removal of iron from a hydrochloric acid waste pickle liquor containing dissolved iron in said waste pickle liquor.
- Waste hydrochloric acid liquors from pickling operations in the iron and steel industry typically contain 20' to 30% by weight of FeCl and one-half to one and onehalf percent acidity as HCl. These liquors may contain small amounts of other metal chlorides, lubricants, inhibitors, hydrocarbons and other organics and impurities. The removal of the iron from the liquor has been a problem of long standing in the industry.
- My invention affords a new and effective method for removal and recovery of the iron oxide while affording a useful liquor residue of CaCl
- This residue liquor can be concentrated and used for control of ice and snow on highways, for dust control on secondary roads, for freeze proofing coal and other ores, and for an addition in concrete mixes to give a quicker initial set.
- the recovered iron oxides being essentially pure, can be utilized in the metal industry as a raw material.
- This invention relates to a process for the treatment of waste hydrochloric acid pickle liquor when a lime slurry and the waste pickle liquor, each being maintained at a temperature of from 180 F. to the boiling point of the liquid are added to a reaction vessel. During the addition and for at least 5 hours thereafter the system is maintained within this temperature range, air is bubbled through this mixture and the mixture is agitated.
- the improvements over known methods are the simultaneous addition of the lime slurry and pickle liquor to the reaction vessel, air oxidation of the dissolved iron to Fe O the maintenance of the resultant mixture at a pH between 8-10 throughout the reaction; the constant agitation of the mixture and the temperature control of the mixture throughout the reaction.
- the system is separated into a solid residue and an aqueous phase.
- the solid residue is comprised essentially of magnetic iron oxide, Fe O
- the aqueous phase is comprised of CaCl in solution.
- the lime slurry used in the practice of this invention consists of from 10 to 30% by weight of calcium hydroxide.
- the function of the air bubbled through the reaction mass is to provide a source of oxygen for the oxidation of the iron salts present in the pickle liquor. Oxygen could also be employed for this purpose but is not preferred because of its higher cost.
- the heat used to raise the solution to a temperature suitable for this reaction can be supplied from any of the readily available sources such as from the coking or smelting operations.
- the process of this invention can be carried on as either a continuous operation or as a batch operation.
- the iron salts present in the waste pickle liquor are oxidized to magnetic iron oxide
- Fe O 99+% of the iron present in the waste pickle liquor is converted to iron oxide crystals which can be separated by physical means such as filtering.
- filter apparatus of the ordinary platen vacuum disc or drum types are suitable. If desired, the iron oxide solids can also be removed by centrifuging.
- Example 1 In a batch operation separate streams of waste pickle liquor containing 20 to 30% ferrous chloride and /2 to 1 /2% hydrochloric acid and a 25% lime slurry stream, each preheated to -200 F. are introduced simultaneously into a reactor equipped with an agitator, air sparge and steam sparge.
- the liquor is fed in at a rate of about 3.8 lb./-min. and the lime slurry at a rate of 2.5 lb./min. with a pH of 8 being maintained in the reactor by adjustment of the liquid flow.
- hold up time is 5 hours. During this time the pH is maintained at 8 and the temperature at 200 F. with constant agitation.
- Air is blown in at the rate of about 8 cu. ft./rnin.
- the slurry is pumped from the reactor to a rotary vacuum drum filter.
- the filter cake contains about 45-50% moisture.
- Example 2 Into a continuous neutralizer containing 300 gallons of agitated reaction slurry at 200 F. and a pH of 8.5 balance streams of lime slurry and picklle liquor are added continuously.
- the lime rate is 13.7 lb. per minute and the acid flow which is automatically regulated by the pH controller, averages 21.4 lb./min. and a small amount of steam is admitted to the slurry to maintain the temperature. Air is sparged continuously into the reactor at 44 c.f.m.
- the slurry is continuously withdrawn to maintain a constant level in the neutralizer. Holdup time in the reactor averages about '5 hours.
- the slurry is fed to a continuous filter which discharges a clear stream of water at a pH of 8.5 and a stream of filter cake, which contains about 45-50% moisture.
- the clear Water contains less than 2 ppm. of iron and about 16.3% calcium chloride. The calcium chloride concentration is dependent upon the amount of condensate in the steam line.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Paper (AREA)
Description
United States Patent 3,434,797 PROCESS FOR TREATMENT OF HYDROCHLORIC ACID WASTE PICKLE LIQUOR Robert A. Taylor, Wilmington, Del., and Frederick G. Krikau, Dolton, 11].; said Taylor assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware, said Krikan assignor to Interlake Steel Corporation, Chicago, Ill., a corporation of New York No Drawing. Filed July 27, 1967, Ser. No. 656,364
Int. Cl. C01f 11/24 US. Cl. 23-90 2 Claims ABSTRACT OF THE DISCLOSURE A process for removal of iron solids from hydrochloric acid Waste pickle liquor by maintaining the system pH between 8-10 while the waste pickle liquor and a lime slurry, each at a temperature of from 180-210 F., are simultaneously introduced into a reaction vessel. The pH and the temperature are maintained for at least hours. The iron is precipitated out as iron oxide crystals (Fe O and is separated from the system by suitable means. The clear liquor contains dissolved calcium chloride.
BACKGROND OF THE INVENTION This invention relates to removal of iron from a hydrochloric acid waste pickle liquor containing dissolved iron in said waste pickle liquor.
Waste hydrochloric acid liquors from pickling operations in the iron and steel industry typically contain 20' to 30% by weight of FeCl and one-half to one and onehalf percent acidity as HCl. These liquors may contain small amounts of other metal chlorides, lubricants, inhibitors, hydrocarbons and other organics and impurities. The removal of the iron from the liquor has been a problem of long standing in the industry.
My invention affords a new and effective method for removal and recovery of the iron oxide while affording a useful liquor residue of CaCl This residue liquor can be concentrated and used for control of ice and snow on highways, for dust control on secondary roads, for freeze proofing coal and other ores, and for an addition in concrete mixes to give a quicker initial set.
The recovered iron oxides, being essentially pure, can be utilized in the metal industry as a raw material.
SUMMARY OF THE INVENTION This invention relates to a process for the treatment of waste hydrochloric acid pickle liquor when a lime slurry and the waste pickle liquor, each being maintained at a temperature of from 180 F. to the boiling point of the liquid are added to a reaction vessel. During the addition and for at least 5 hours thereafter the system is maintained within this temperature range, air is bubbled through this mixture and the mixture is agitated.
The improvements over known methods are the simultaneous addition of the lime slurry and pickle liquor to the reaction vessel, air oxidation of the dissolved iron to Fe O the maintenance of the resultant mixture at a pH between 8-10 throughout the reaction; the constant agitation of the mixture and the temperature control of the mixture throughout the reaction.
At the end of at least 5 hours the system is separated into a solid residue and an aqueous phase. The solid residue is comprised essentially of magnetic iron oxide, Fe O The aqueous phase is comprised of CaCl in solution.
It is necessary that the pH of the reaction mixture be maintained at 8 or above to accomplish the almost total recovery of the dissolved iron from the pickle liquor. It
has been found that a pH lower than 8 will result in substantially reduced iron recovered from the Waste pickle liquor. It is believed that this is a result of the effect of the chloride ion on the solubility of the iron. Therefore, it is essential to operate the process of this invention at a pH of 8 or above in order to recover up to 99+% of the iron content of the waste pickle liquor.
The lime slurry used in the practice of this invention consists of from 10 to 30% by weight of calcium hydroxide.
The function of the air bubbled through the reaction mass is to provide a source of oxygen for the oxidation of the iron salts present in the pickle liquor. Oxygen could also be employed for this purpose but is not preferred because of its higher cost.
The heat used to raise the solution to a temperature suitable for this reaction can be supplied from any of the readily available sources such as from the coking or smelting operations.
It is also possible to employ the instant process when the pickle liquor employed is a mixture of sulfuric and hydrochloric acids with equally successful results as when the pickle liquor is hydrochloric acid alone.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The process of this invention can be carried on as either a continuous operation or as a batch operation. In each type operation the iron salts present in the waste pickle liquor are oxidized to magnetic iron oxide, Fe O 99+% of the iron present in the waste pickle liquor is converted to iron oxide crystals which can be separated by physical means such as filtering. For this purpose filter apparatus of the ordinary platen, vacuum disc or drum types are suitable. If desired, the iron oxide solids can also be removed by centrifuging.
The following examples are presented to illustrate the operation of the process of this invention:
Example 1 In a batch operation separate streams of waste pickle liquor containing 20 to 30% ferrous chloride and /2 to 1 /2% hydrochloric acid and a 25% lime slurry stream, each preheated to -200 F. are introduced simultaneously into a reactor equipped with an agitator, air sparge and steam sparge. The liquor is fed in at a rate of about 3.8 lb./-min. and the lime slurry at a rate of 2.5 lb./min. with a pH of 8 being maintained in the reactor by adjustment of the liquid flow. After the reactor is filled, hold up time is 5 hours. During this time the pH is maintained at 8 and the temperature at 200 F. with constant agitation. Air is blown in at the rate of about 8 cu. ft./rnin. After 5 hours have elapsed the slurry is pumped from the reactor to a rotary vacuum drum filter. The filter cake contains about 45-50% moisture.
Example 2 Into a continuous neutralizer containing 300 gallons of agitated reaction slurry at 200 F. and a pH of 8.5 balance streams of lime slurry and picklle liquor are added continuously. The lime rate is 13.7 lb. per minute and the acid flow which is automatically regulated by the pH controller, averages 21.4 lb./min. and a small amount of steam is admitted to the slurry to maintain the temperature. Air is sparged continuously into the reactor at 44 c.f.m.
The slurry is continuously withdrawn to maintain a constant level in the neutralizer. Holdup time in the reactor averages about '5 hours. The slurry is fed to a continuous filter which discharges a clear stream of water at a pH of 8.5 and a stream of filter cake, which contains about 45-50% moisture. The clear Water contains less than 2 ppm. of iron and about 16.3% calcium chloride. The calcium chloride concentration is dependent upon the amount of condensate in the steam line.
We claim:
1. In a process for the treatment of a hydrochloric acid Waste pickle liquor containing FeCl by adding a lime slurry and the pickle liquor to a reaction vessel, to form insoluble iron oxide (Fe O and then separating the resultant solid phase and aqueous phase the improvements comprising:
(a) simultaneously adding the Waste pickle liquor and lime slurry to the reaction vessel each being heated to a temperature of from 180 F. to the boiling point of the liquid;
(b) bubbling air through this mixture;
(c) maintaining the mixture at a pH of from 8 to 10 at all times during the reaction;
(d) agitating the mixture during the reaction;
(e) maintaining the mixture at a temperature of from 180 F. to the boiling point of the mixture; and
(f) the conditions of (b), (c), (d), and (e) above being maintained for at least 5 hours.
2. The process of claim 1 wherein the pH of the Waste pickle liquor-lime slurry mixture is maintained at 8.5 and the temperature is maintained at 200 F. for 5 hours.
References Cited OTHER REFERENCES Hoak et al.: Lime Treatment of Waste Pickle Liquor, Industrial and Engineering Chemistry, vol. 39, No. 2, February 1947, pp. 131-135, inclusive.
EDWARD STERN, Primary Examiner.
US. Cl. X.R. 23-122, 200
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65636467A | 1967-07-27 | 1967-07-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3434797A true US3434797A (en) | 1969-03-25 |
Family
ID=24632715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US656364A Expired - Lifetime US3434797A (en) | 1967-07-27 | 1967-07-27 | Process for treatment of hydrochloric acid waste pickle liquor |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3434797A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115106A (en) * | 1976-10-20 | 1978-09-19 | National Standard Company | Method for producing metallic oxide compounds |
| DE3004718A1 (en) * | 1979-02-09 | 1980-08-14 | Pfizer | SYNTHETIC, RHOMBOEDRIC MAGNETITE PIGMENT |
| US4382822A (en) * | 1979-09-14 | 1983-05-10 | Pfizer Inc. | Synthetic rhombohedral magnetite pigment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1287939A (en) * | 1917-12-20 | 1918-12-17 | Magnetic Pigment Company | Utilization of sulfuric-acid pickle liquors. |
| US2423385A (en) * | 1944-07-27 | 1947-07-01 | Chemical Foundation Inc | Process of pickling and of recovering pickling agent |
| US2433458A (en) * | 1943-03-04 | 1947-12-30 | Infilco Inc | Treatment of pickle liquor |
| US2636807A (en) * | 1951-10-09 | 1953-04-28 | Gen Electric | Purification of calcium chloride |
| US3261665A (en) * | 1962-11-05 | 1966-07-19 | Du Pont | Process for the treatment of waste sulfuric acid pickle liquor |
-
1967
- 1967-07-27 US US656364A patent/US3434797A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1287939A (en) * | 1917-12-20 | 1918-12-17 | Magnetic Pigment Company | Utilization of sulfuric-acid pickle liquors. |
| US2433458A (en) * | 1943-03-04 | 1947-12-30 | Infilco Inc | Treatment of pickle liquor |
| US2423385A (en) * | 1944-07-27 | 1947-07-01 | Chemical Foundation Inc | Process of pickling and of recovering pickling agent |
| US2636807A (en) * | 1951-10-09 | 1953-04-28 | Gen Electric | Purification of calcium chloride |
| US3261665A (en) * | 1962-11-05 | 1966-07-19 | Du Pont | Process for the treatment of waste sulfuric acid pickle liquor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115106A (en) * | 1976-10-20 | 1978-09-19 | National Standard Company | Method for producing metallic oxide compounds |
| DE3004718A1 (en) * | 1979-02-09 | 1980-08-14 | Pfizer | SYNTHETIC, RHOMBOEDRIC MAGNETITE PIGMENT |
| FR2448559A1 (en) * | 1979-02-09 | 1980-09-05 | Pfizer | SYNTHETIC RHOMBOEDRIC MAGNETITE PIGMENT AND PROCESS FOR OBTAINING SAME |
| US4382822A (en) * | 1979-09-14 | 1983-05-10 | Pfizer Inc. | Synthetic rhombohedral magnetite pigment |
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